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WO2021241870A1 - Composition de résine thermoplastique pour un procédé de structuration directe par laser et produit moulé la comprenant - Google Patents

Composition de résine thermoplastique pour un procédé de structuration directe par laser et produit moulé la comprenant Download PDF

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Publication number
WO2021241870A1
WO2021241870A1 PCT/KR2021/003743 KR2021003743W WO2021241870A1 WO 2021241870 A1 WO2021241870 A1 WO 2021241870A1 KR 2021003743 W KR2021003743 W KR 2021003743W WO 2021241870 A1 WO2021241870 A1 WO 2021241870A1
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resin composition
thermoplastic resin
weight
parts
laser direct
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English (en)
Korean (ko)
Inventor
김남현
강태곤
김태윤
우은택
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Lotte Chemical Corp
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Lotte Chemical Corp
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Priority to CN202180038289.4A priority Critical patent/CN115702208B/zh
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2026—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by radiant energy
    • C23C18/204—Radiation, e.g. UV, laser

Definitions

  • the present invention relates to a thermoplastic resin composition for laser direct structuring and a molded article comprising the same. More specifically, the present invention relates to a thermoplastic resin composition for a laser direct structuring process having excellent plating reliability, impact resistance, chemical resistance (impact resistance to thin film after coating), rigidity, and thin film formability, and a molded article including the same.
  • a laser direct structuring process is a process performed before the plating step, and by irradiating a laser to the plating target area of the surface of the molded article, it means a process of modifying the plating target area on the surface of the molded article to have properties suitable for plating.
  • the thermoplastic resin composition for manufacturing a molded article must contain an additive for laser direct structuring (LDS additive) capable of forming metal nuclei by laser.
  • the additive generates metal nuclei while decomposing when subjected to a laser.
  • the area irradiated with the laser has a roughened surface. Due to these metal nuclei and surface roughness, the laser-modified area becomes suitable for plating.
  • the laser direct structuring process may be utilized in manufacturing an antenna of a portable electronic device, a radio frequency identification (RFID) antenna, and the like.
  • RFID radio frequency identification
  • thermoplastic resin composition having excellent mechanical properties and molding processability is required.
  • a plating peeling phenomenon may occur, which may reduce plating reliability.
  • thermoplastic resin composition for laser direct structuring process with excellent plating reliability, impact resistance, chemical resistance (impact resistance to thin film after coating), rigidity, thin film formability, and the like, and a molded article including the same.
  • thermoplastic resin composition excellent in plating reliability, impact resistance, chemical resistance (impact resistance of a thin film after coating), rigidity, thin film formability, and the like.
  • Another object of the present invention is to provide a molded article formed from the thermoplastic resin composition.
  • thermoplastic resin composition comprises about 100 parts by weight of a polycarbonate resin; About 10 to about 50 parts by weight of a glycol-modified polyester resin having a 1,4-cyclohexanedimethanol content of about 20 to about 100 mol% of the total diol component; about 5 to about 25 parts by weight of an additive for laser direct structuring; About 1 to about 9 parts by weight of a modified polyolefin comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2); about 5 to about 9 parts by weight of a phosphorus-based compound comprising about 60 to about 90% by weight of a phosphate compound and about 10 to about 40% by weight of a phosphazene compound; and about 20 to about 70 parts by weight of glass fiber, wherein the weight ratio of the additive for laser direct structuring and the phosphorus compound is about 1:0.25 to about 1:1.20.
  • R 1 is a hydrogen atom or a methyl group
  • Y is -COOR 2 (R 2 is an alkyl group having 1 to 12 carbon atoms), a glycidyl-modified ester group, an arylate group, or a nitrile group (-CN) .
  • the additive for laser direct structuring may include at least one of a heavy metal complex oxide spinel and a copper salt.
  • the modified olefin may include about 50 to about 95 wt% of the repeating unit represented by Formula 1 and about 5 to about 50 wt% of the repeating unit represented by Formula 2 .
  • the modified polyolefin comprises at least one of ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), and ethylene-butyl acrylate (EBA). can do.
  • EMA ethylene-methyl acrylate copolymer
  • EAA ethylene-ethyl acrylate copolymer
  • EBA ethylene-butyl acrylate
  • the weight ratio of the glycol-modified polyester resin and the additive for laser direct structuring may be about 1: 0.15 to about 1:1.
  • the thermoplastic resin composition is a 50 mm ⁇ 90 mm ⁇ 3.2 mm injection-molded specimen after aging at 25° C. for 6 hours, and then stripes through a laser direct structuring process.
  • the plated specimen was placed in a chamber at 85° C. and 85% RH for 120 hours.
  • the number of grid grids that are not peeled off when detached with a tape may be about 90 to about 100.
  • thermoplastic resin composition may have a notch Izod impact strength of about 6 to about 20 kgf ⁇ cm/cm of a 1/8′′ thick specimen measured according to ASTM D256.
  • thermoplastic resin composition is obtained by immersing a 1 mm thick specimen in a thinner solution for 2 minutes and 30 seconds, drying it at 80° C. for 20 minutes, leaving it at room temperature for 24 hours, and then adding a weight of 500 g
  • the height at which the specimen is destroyed may be about 47 to about 70 cm.
  • thermoplastic resin composition may have a flexural modulus of about 50,000 to about 70,000 kgf/cm 2 of a specimen having a thickness of 1/4” measured according to ASTM D790.
  • the thermoplastic resin composition is a spiral having a width of 15 mm and a thickness of 0.5 mm under the conditions of a molding temperature of 320° C., a mold temperature of 60° C., an injection pressure of 100 MPa, and an injection speed of 100 mm/s. ), the length of the spiral flow of the specimen measured after injection molding in the mold may be about 110 to about 180 mm.
  • Another aspect of the present invention relates to a molded article.
  • the molded article is characterized in that it is formed from the thermoplastic resin composition according to any one of 1 to 10.
  • the molded article may include a metal layer formed on at least a portion of the surface by a laser direct structuring process and a plating process.
  • the present invention has the effect of providing a thermoplastic resin composition excellent in plating reliability, impact resistance, chemical resistance (impact resistance to thin film after coating), rigidity, thin film formability, and the like, and a molded article formed therefrom.
  • FIG. 1 schematically shows a molded article according to an embodiment of the present invention.
  • thermoplastic resin composition according to the present invention can be used in a laser direct structuring process (LDS process), (A) a polycarbonate resin; (B) glycol-modified polyester resin; (C) additives for laser direct structuring (LDS); (D) modified polyolefins; and (E) a phosphorus-based compound; and (F) glass fibers.
  • LDS process a laser direct structuring process
  • A a polycarbonate resin
  • B glycol-modified polyester resin
  • C additives for laser direct structuring
  • D modified polyolefins
  • E a phosphorus-based compound
  • glass fibers glass fibers.
  • a polycarbonate resin used in a conventional thermoplastic resin composition may be used.
  • an aromatic polycarbonate resin produced by reacting diphenols (aromatic diol compounds) with a carbonate precursor can be used.
  • the diphenols include 4,4'-biphenol, 2,2-bis(4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1 ,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl) Propane and the like may be exemplified, but the present invention is not limited thereto.
  • 2,2-bis(4-hydroxyphenyl)propane 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, or 1,1-bis(4-hydroxyphenyl)propane ) cyclohexane, and specifically, 2,2-bis(4-hydroxyphenyl)propane called bisphenol-A may be used.
  • the carbonate precursor is dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate , carbonyl chloride (phosgene), diphosgene, triphosgene, carbonyl bromide, bishaloformate, and the like can be exemplified. These can be used individually or in mixture of 2 or more types.
  • the polycarbonate resin may be one having a branched chain, for example, based on the total amount of diphenols used for polymerization, from about 0.05 to about 2 mol% of a trivalent or higher polyfunctional compound, specifically , a branched polycarbonate resin prepared by adding a compound having a trivalent or higher phenol group may be used.
  • the polycarbonate resin may be used in the form of a homo polycarbonate resin, a copolycarbonate resin, or a blend thereof.
  • the polycarbonate resin may be partially or entirely replaced with an aromatic polyester-carbonate resin obtained by polymerization in the presence of an ester precursor, for example, a bifunctional carboxylic acid.
  • the polycarbonate resin may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of about 10,000 to about 200,000 g/mol, for example, about 15,000 to about 80,000 g/mol.
  • Mw weight average molecular weight measured by gel permeation chromatography
  • the thermoplastic resin composition may have excellent mechanical properties, fluidity (processability), and the like.
  • the glycol-modified polyester resin according to an embodiment of the present invention is applied together with a modified polyolefin, a specific phosphorus compound and glass fiber, and the plating reliability, chemical resistance (impact resistance of the thin film after coating) of the thermoplastic resin composition for laser direct structuring process, As one capable of improving thin film formability (fluidity), etc., a glycol-modified polyester resin having a 1,4-cyclohexanedimethanol content of about 20 to about 100 mol% among the total diol components may be used.
  • the glycol-modified polyester resin is a dicarboxylic acid component including terephthalic acid and 1,4-cyclohexanedimethanol (CHDM) about 20 to about 100 mol%, for example, about 35 to about 100 mol% and about 80 mol% or less of an alkylene glycol having 2 to 6 carbon atoms, for example, about 65 mol% or less.
  • CHDM 1,4-cyclohexanedimethanol
  • the glycol-modified polyester resin has an intrinsic viscosity of about 0.5 to about 0.8 dl/g, for example about 0.55 to about 0.8 dl/g, measured at 35° C. using an o-chlorophenol solution (concentration: 1.2 g/dl). about 0.75 dl/g.
  • miscibility between the components of the thermoplastic resin composition may be improved, and the thermoplastic resin composition may have excellent mechanical properties, molding processability (fluidity), and the like.
  • the glycol-modified polyester resin may be included in an amount of about 10 to about 50 parts by weight, for example, about 15 to about 40 parts by weight, based on about 100 parts by weight of the polycarbonate resin.
  • the content of the glycol-modified polyester resin is less than about 10 parts by weight with respect to about 100 parts by weight of the polycarbonate resin, there is a risk that the plating reliability and thin film moldability of the thermoplastic resin composition may be deteriorated, and it exceeds about 50 parts by weight In this case, there is a fear that the chemical resistance, impact resistance, etc. of the thermoplastic resin composition may be lowered.
  • the additive for laser direct structuring is capable of forming metal nuclei by laser, and is an additive for laser direct structuring used in a conventional resin composition for laser direct structuring.
  • the laser refers to light (induced emission light) amplified by stimulated emission
  • the laser is an ultraviolet light having a wavelength of 100 to 400 nm, visible light having a wavelength of 400 to 800 nm, or infrared light having a wavelength of 800 to 25,000 nm. It may be, for example, may be an infrared ray of a wavelength of 1,000 to 2,000 nm.
  • the additive for laser direct structuring may include a heavy metal mixture oxide spinel and/or a copper salt.
  • the heavy metal composite oxide spinel is magnesium aluminum oxide (MgAl 2 O 4 ), zinc aluminum oxide (ZnAl 2 O 4 ), iron aluminum oxide (FeAl 2 O 4 ), copper iron oxide (CuFe 2 O 4 ) , copper chromium oxide (CuCr 2 O 4 ), manganese iron oxide (MnFe 2 O 4 ), nickel iron oxide (NiFe 2 O 4 ), titanium iron oxide (TiFe 2 O 4 ), iron chromium oxide (FeCr 2 O 4 ) , magnesium chromium oxide (MgCr 2 O 4 ), and combinations thereof.
  • copper chromium oxide (CuCr 2 O 4 ) may be used. Since the copper chromium oxide (CuCr 2 O 4 ) has a dark color, it can be applied when the color required for the final molded product is a dark color such as black or gray.
  • copper hydroxide phosphate copper hydroxide phosphate
  • copper phosphate copper phosphate
  • copper sulfate cuprous thiocyanate
  • cuprous thiocyanate cuprous thiocyanate thereof Combinations may be exemplified, but the present invention is not limited thereto.
  • copper hydroxide phosphate can be used.
  • the copper hydroxide phosphate (copper hydroxide phosphate) is a compound in which copper phosphate and copper hydroxide are bonded, specifically Cu 3 (PO 4 ) 2 ⁇ 2Cu(OH) 2 , Cu 3 (PO 4 ) 2 ⁇ Cu(OH) 2 and the like.
  • the copper hydroxide phosphate does not reduce the color reproducibility of an additionally added colorant, so that a molded article of a desired color can be easily obtained.
  • the additive for laser direct structuring may have an average particle diameter of about 0.01 to about 50 ⁇ m, for example, about 0.1 to about 30 ⁇ m, specifically about 0.5 to about 10 ⁇ m.
  • the plating surface may be uniformly formed during plating through laser direct structuring.
  • the average particle diameter is the number average diameter and means that D50 (the particle diameter at the point where the distribution ratio is 50%) is measured.
  • the additive for laser direct structuring may be included in an amount of about 5 to about 25 parts by weight, for example, about 6 to about 24 parts by weight based on 100 parts by weight of the polycarbonate resin.
  • the content of the laser direct structuring additive is less than about 5 parts by weight based on about 100 parts by weight of the polycarbonate resin, when irradiating the thermoplastic resin composition (molded article) with a laser, a sufficient amount of metal nuclei is not formed for plating. Otherwise, there is a fear that plating reliability may be lowered, and when it exceeds about 25 parts by weight, plating reliability, impact resistance, etc. of the thermoplastic resin composition may be deteriorated.
  • the weight ratio (B:C) of the glycol-modified polyester resin and the additive for laser direct structuring may be about 1: 0.15 to about 1:1, for example, about 1: 0.2 to about 1: 0.96. .
  • the plating reliability, chemical resistance, thin film moldability, etc. of the thermoplastic resin composition may be excellent.
  • the modified polyolefin according to an embodiment of the present invention is applied together with a glycol-modified polyester resin, a specific phosphorus compound, and glass fiber, and the plating reliability, impact resistance, and chemical resistance of the thermoplastic resin composition for laser direct structuring process (in the thin film after painting) impact property), thin film formability (fluidity), etc., and functional groups (alkyl carboxylate group, glycidyl-modified ester group, arylate group, nitrile group, etc.) It may have a structure containing
  • a modified polyolefin including a repeating unit represented by the following Chemical Formula 1 and a repeating unit represented by the following Chemical Formula 2 may be used.
  • R 1 is a hydrogen atom or a methyl group
  • Y is -COOR 2 (R 2 is an alkyl group having 1 to 12 carbon atoms), a glycidyl-modified ester group, an arylate group, or a nitrile group (-CN) .
  • the modified polyolefin may be prepared by polymerizing at least one compound of an olefin and an alkyl (meth)acrylate, a modified ester containing an ethylenically unsaturated group, an arylate containing an ethylenically unsaturated group, and an acrylonitrile.
  • a modified polyolefin prepared by polymerization of an olefin and an alkyl (meth)acrylate may be applied.
  • the modified polyolefin may include at least one of ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), and ethylene-butyl acrylate (EBA).
  • the modified olefin comprises about 50 to about 95 wt% of the repeating unit represented by Formula 1, for example, about 70 to about 93 wt%, and about 5 to about 50 wt% of the repeating unit represented by Formula 2 , for example, about 7 to about 30% by weight.
  • the thermoplastic resin composition may have excellent impact resistance, fluidity (molding processability), compatibility, and the like.
  • the modified polyolefin may be in the form of a random, block, or multi-block copolymer, or a combination thereof.
  • the modified polyolefin has a melt flow index of about 0.01 to about 40 g/10 min, for example, about 0.1 to about 10 g/10 min, measured at 190° C. and 2.16 kgf, according to ASTM D1238.
  • the modified polyolefin may be included in an amount of about 1 to about 9 parts by weight, for example, about 2 to about 8 parts by weight, based on 100 parts by weight of the polycarbonate resin.
  • the content of the modified polyolefin is less than about 1 part by weight based on about 100 parts by weight of the polycarbonate resin, there is a risk that the impact resistance and chemical resistance of the thermoplastic resin composition may be lowered, and when it exceeds about 9 parts by weight, the thermoplastic resin composition The rigidity, plating reliability, thin film formability, etc. of a resin composition may fall.
  • the phosphorus compound of the present invention is applied together with glycol-modified polyester resin, modified polyolefin, and glass fiber, and the plating reliability, impact resistance, and chemical resistance of the thermoplastic resin composition for laser direct structuring process (thin film impact resistance after painting), thin film formability (fluidity) and the like, for example, about 60 to about 90% by weight of a phosphate compound, for example about 65 to about 85% by weight, and about 10 to about 40% by weight of a phosphazene compound, such as about 15 to about 35% by weight.
  • the content of the phosphate compound in the phosphorus compound is less than about 60% by weight (the content of the phosphazene compound is greater than about 40% by weight), there is a risk that the chemical resistance of the thermoplastic resin composition may decrease, and the phosphate compound in the phosphorus compound When the content of is greater than about 90% by weight (the content of the phosphazene compound is less than about 10% by weight), there is a fear that the thin film formability of the thermoplastic resin composition may be deteriorated.
  • the phosphate compound may include a compound represented by Formula 3 below.
  • R 1 , R 2 , R 4 and R 5 are each independently a hydrogen atom, a C6-C20 (C6-C20 aryl group, or a C1-C10 alkyl group-substituted C6-C20 aryl group).
  • a group, and R 3 is a C6-C20 arylene group or a C6-C20 arylene group substituted with a C1-C10 alkyl group, for example, a dialcohol such as resorcinol, hydroquinone, bisphenol-A, or bisphenol-S. It is derived from, and n is an integer of 0 to 10, for example 0 to 4.
  • diaryl phosphate such as diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, trizyrenyl phosphate, tri (2,6-dimethylphenyl) phosphate , tri(2,4,6-trimethylphenyl)phosphate, tri(2,4-ditertibutylphenyl)phosphate, tri(2,6-dimethylphenyl)phosphate, and the like
  • n is 1, Bisphenol-A bis(diphenylphosphate), resorcinol bis(diphenylphosphate), resorcinol bis[bis(2,6-dimethylphenyl)phosphate], resorcinol bis[bis(2,4-detertiary) butylphenyl)phosphate], hydroquinone bis[bis(2,6-dimethylphenyl)phosphate], hydroquinone bis(diphenylphosphate), hydroquinone bis[bis(2,6-dimethylphenyl)phosphate], hydroquino
  • the phosphazene compound may include a compound represented by Formula 4 below.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted An alkenyl group having 2 to 7 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aryloxy group, a heteroaryl group having 5 to 20 carbon atoms, a substituted or unsubstituted alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted carbonylalkyl group having 2 to 10 carbon atoms, an amino group or a
  • substitution refers to an alkyl group having 1 to 10 carbon atoms, a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms. It means being substituted with a substituent such as a heterocycloalkyl group, a heteroaryl group having 4 to 10 carbon atoms, or a combination thereof.
  • alkyl alkoxy and other substituents containing “alkyl” moieties include both straight-chain or branched forms, and “alkenyl” has 2 to 8 carbon atoms and contains one or more double bonds. includes both straight-chain or pulverized forms, and the term “cycloalkyl” includes both saturated monocyclic or saturated bicyclic ring structures having 3 to 20 carbon atoms.
  • the "aryl” is an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen atom, and represents a single or fused ring system comprising suitably 4 to 7, preferably 5 or 6 ring atoms in each ring. include Specifically, phenyl, naphthyl, biphenyl, tolyl, and the like can be exemplified.
  • heterocycloalkyl refers to a cycloalkyl group comprising 1 to 3 heteroatoms selected from N, O, S as saturated cyclic hydrocarbon backbone atoms, and the remaining saturated monocyclic or bicyclic ring backbone atoms are carbon.
  • pyrrolidinyl, azetidinyl, pyrazolidinyl, oxazolidinyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, thiazolidinyl, hydantoinyl, valerolactamyl, Oxiranyl, oxetanyl, dioxolanyl, dioxanyl, oxathiolanyl, oxathianyl, dithianyl, dihydrofuranyl, tetrahydrofuranyl, dihydropyranyl, tetrahydropyranyl, tetrahydropyri dinyl, tetrahydropyrimidinyl, tetrahydrothiophenyl, tetrahydrothiopyranyl, diazepanyl, azepanyl and the like can be exemplified.
  • heteroaryl refers to an aryl group containing 1 to 3 heteroatoms selected from N, O, and S as an aromatic ring skeleton atom, and the remaining aromatic ring skeleton atoms are carbon, wherein the heteroaryl group is a heteroaryl group and divalent aryl groups in which atoms are oxidized or quaternized to form, for example, N-oxides or quaternary salts.
  • the phosphorus-based compound may be included in an amount of about 5 to about 9 parts by weight, for example, about 6 to about 8 parts by weight, based on about 100 parts by weight of the polycarbonate resin.
  • the content of the phosphorus compound is less than about 5 parts by weight based on about 100 parts by weight of the polycarbonate resin, there is a risk that the thin film formability of the thermoplastic resin composition may be deteriorated, and when it exceeds about 9 parts by weight, the thermoplastic resin composition plating reliability, chemical resistance, etc. may be reduced.
  • the weight ratio (C:E) of the additive for laser direct structuring and the phosphorus-based compound may be from about 1:0.25 to about 1:1.20, for example, from about 1:0.4 to about 1:1.17.
  • the weight ratio of the laser direct structuring additive and the phosphorus compound is less than about 1:0.25, there is a risk that the thin film formability of the thermoplastic resin composition may deteriorate, and if it exceeds about 1:1.20, the plating reliability of the thermoplastic resin composition , there is a possibility that chemical resistance, impact resistance, etc. may be lowered.
  • Glass fiber according to an embodiment of the present invention is applied together with glycol-modified polyester resin, modified polyolefin, and specific phosphorus-based compounds, so that the plating reliability, impact resistance, and chemical resistance (in the thin film after coating) of the thermoplastic resin composition for laser direct structuring process Impact property), rigidity, thin film formability (fluidity), etc. can be improved, and glass fibers used in conventional thermoplastic resin compositions can be used.
  • the glass fiber may be in the form of a fiber, and may have a cross section of various shapes, such as a circle, an oval, and a rectangle.
  • a cross section of various shapes such as a circle, an oval, and a rectangle.
  • fibrous glass fibers of circular and/or rectangular cross-section may be preferable in view of mechanical properties.
  • the glass fiber of the circular cross-section may have a cross-sectional diameter of about 5 to about 20 ⁇ m and a length before processing of about 2 to about 20 mm measured by an optical microscope, and the glass fiber of the rectangular cross-section is measured by an optical microscope
  • the measured aspect ratio of the cross-section may be about 1.5 to about 10
  • the minor diameter may be about 2 to about 10 ⁇ m
  • the length before processing may be about 2 to about 20 mm.
  • dimensional stability, rigidity, processability, etc. of the thermoplastic resin composition may be improved.
  • the glass fiber may be treated with a conventional surface treatment agent.
  • the glass fiber may be included in an amount of about 20 to about 70 parts by weight, for example, about 30 to about 60 parts by weight, based on about 100 parts by weight of the polycarbonate resin.
  • the content of the glass fiber is less than about 20 parts by weight based on about 100 parts by weight of the polycarbonate resin, there is a risk that the rigidity of the thermoplastic resin composition may decrease, and when it exceeds about 70 parts by weight, the plating of the thermoplastic resin composition Reliability, thin film formability, etc. may fall.
  • the weight ratio (B:F) of the glycol-modified polyester resin and the glass fiber may be from about 1:0.6 to about 1:6, for example, from about 1:1 to about 1:3. In the above range, plating reliability, thin film fluidity, chemical resistance, and the like of the thermoplastic resin composition may be more excellent.
  • the thermoplastic resin composition according to an embodiment of the present invention may further include an additive included in a conventional thermoplastic resin composition.
  • the additive include, but are not limited to, inorganic fillers, anti-drip agents, lubricants, nucleating agents, stabilizers, release agents, pigments, dyes, and mixtures thereof.
  • its content may be from about 0.001 to about 40 parts by weight, for example, from about 0.1 to about 10 parts by weight, based on 100 parts by weight of the polycarbonate resin.
  • thermoplastic resin composition according to an embodiment of the present invention is in the form of pellets that are melt-extruded at about 200 to about 280 ° C, for example, about 220 to about 260 ° C, by mixing the above components and using a conventional twin screw extruder.
  • the thermoplastic resin composition is a 50 mm ⁇ 90 mm ⁇ 3.2 mm injection-molded specimen after aging at 25° C. for 6 hours, and then the surface of the specimen in a stripe shape through a laser direct structuring process. After activation, a copper layer with a thickness of 35 ⁇ m is formed on the activated surface through a plating process (copper electroless plating), and the plated specimen is left in a chamber at 85° C. and 85% RH for 120 hours, and 1 mm After engraving 100 grid grids with a size of ⁇ 1 mm on the plating layer (copper layer), the number of grid grids that are not peeled off when detached with tape is about 90 to about 100, for example, about 92 to about 100 days can
  • the thermoplastic resin composition has a notch Izod impact strength of about 6 to about 20 kgf ⁇ cm/cm, for example, about 6 to about 11 kgf ⁇ cm, of a 1/8′′ thick specimen measured according to ASTM D256. It can be /cm.
  • the thermoplastic resin composition is a specimen having a thickness of 1 mm or less, immersed in a thinner solution for 2 minutes and 30 seconds, dried at 80° C. for 20 minutes, left at room temperature for 24 hours, and then DuPont using a 500 g weight.
  • the height at which the specimen is destroyed by impact with a drop test method of falling weight evaluation equipment may be about 47 to about 70 cm, for example, about 50 to about 65 cm.
  • the thermoplastic resin composition has a flexural modulus of about 50,000 to about 70,000 kgf/cm 2 , for example, about 50,000 to about 65,000 kgf/cm 2 , of a thickness 1/4” specimen measured according to ASTM D790. have.
  • the thermoplastic resin composition is injected in a spiral mold having a width of 15 mm and a thickness of 0.5 mm under the conditions of a molding temperature of 320° C., a mold temperature of 60° C., an injection pressure of 100 MPa and an injection speed of 100 mm/s.
  • a spiral flow length of the specimen measured after molding may be about 110 to about 180 mm, for example, about 112 to about 150 mm.
  • the molded article according to the present invention is formed from the thermoplastic resin composition.
  • a molded article may be manufactured by a molding method such as injection molding, compression molding, blow molding, or extrusion molding.
  • the molded article may be easily formed by a person skilled in the art to which the present invention pertains.
  • the molded article 10 may include a metal layer 20 formed on at least a portion of the surface of the molded article 10 by a laser direct structuring process and a plating process.
  • the molded article 10 may be a circuit carrier used to manufacture an antenna, and the molded article 10 is, for example, a molded article ( 10) was prepared; irradiating a laser to a specific area (a portion of the metal layer 20) on the surface of the molded article 10; It may be manufactured by metallizing (plating) the irradiated area to form the metal layer 20 .
  • the laser direct structuring additive included in the molded article 10 is decomposed by the laser irradiation to generate metal nuclei.
  • the laser-irradiated area has a surface roughness suitable for plating.
  • the wavelength of the laser may be 248 nm, 308 nm, 355 nm, 532 nm, 1,064 nm or 10,600 nm.
  • the metallization process may be performed through a conventional plating process.
  • the metal layer 20 (electrically conductive path) may be formed on the laser-irradiated region of the surface of the molded article 10 by immersing the laser-irradiated molded article 10 in one or more electroless plating baths.
  • the plating process may include a copper plating process, a gold plating process, a nickel plating process, silver plating, zinc plating, tin plating, and the like.
  • a molded article in which a metal layer is formed on at least a portion of a surface by a laser direct structuring process can be easily formed by a person skilled in the art to which the present invention pertains.
  • Bisphenol-A type polycarbonate resin having a weight average molecular weight (Mw) of 25,000 g/mol was used.
  • Copper hydroxide phosphate (manufacturer: Merck performance materials) was used.
  • Glass fiber (manufacturer: KCC, product name: CS321-EC10-3) was used.
  • extrusion was performed at 250° C. to prepare pellets.
  • the prepared specimens were evaluated for physical properties by the following method, and the results are shown in Tables 1, 2, 3 and 4 below.
  • Thin film formability (fluidity) evaluation A spiral mold with a width of 15 mm and a thickness of 0.5 mm under the conditions of a molding temperature of 320°C, a mold temperature of 60°C, an injection pressure of 100 MPa, and an injection speed of 100 mm/s. After injection molding, the length (unit: mm) of the spiral flow of the specimen was measured.
  • Example One 2 3 4 5 6 7 (A) (parts by weight) 100 100 100 100 100 100 100 100 100 100 100 (B1) (parts by weight) 15 25 40 25 25 25 25 (B2) (parts by weight) - - - - - - - (C) (parts by weight) 13 13 13 6 24 13 13 (D1) (parts by weight) 4 4 4 4 4 2 8 (D2) (parts by weight) - - - - - - - (E) (parts by weight) 7 7 7 7 7 7 7 (E1) (wt%) 75 75 75 75 75 75 75 75 75 75 75 75 (E2) (wt%) 25 25 25 25 25 25 25 25 (E3) (wt%) - - - - - - - - (F) (parts by weight) 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 Number of unexfoli
  • comparative example 9 10 11 12 13 14 15 (A) (parts by weight) 100 100 100 100 100 100 100 100 100 100 100 (B1) (parts by weight) 25 25 25 25 25 25 25 25 25 25 (B2) (parts by weight) - - - - - - - (C) (parts by weight) 13 13 13 13 13 13 13 (D1) (parts by weight) 4 4 4 4 4 4 4 4 (D2) (parts by weight) - - - - - - - (E) (parts by weight) 4 10 7 7 7 7 7 (E1) (wt%) 75 75 50 95 - 75 75 (E2) (wt%) 25 25 50 5 - 25 25 (E3) (wt%) - - - - 100 - - (F) (parts by weight) 40 40 40 40 40 10 80 Number of unexfoliated grid grids (pieces) 100 78 100 100 100 88 100 72 Notched Izod impact strength (kgf cm/cm) 8.0 6.6
  • thermoplastic resin composition of the present invention has excellent plating reliability, impact resistance, chemical resistance (impact resistance of a thin film after coating), rigidity, and thin film formability (fluidity).
  • Comparative Example 1 in which a small amount of glycol-modified polyester resin is applied, it can be seen that plating reliability and thin film formability are lowered, and in Comparative Example 2 in which an excessive amount of glycol-modified polyester resin is applied, chemical resistance, impact resistance, etc. It can be seen that the deterioration, in the case of Comparative Example 3 in which polyethylene terephthalate (B2) is applied instead of the glycol-modified polyester resin of the present invention, plating reliability, chemical resistance, and the like are lowered. In the case of Comparative Example 4, in which a small amount of the additive for laser direct structuring was applied, the plating properties were lowered and non-plating occurred. have.
  • Comparative Example 6 In the case of Comparative Example 6 in which a small amount of the modified polyolefin of the present invention is applied, it can be seen that the impact resistance and the like are lowered and the chemical resistance is rapidly reduced. It can be seen that the thin film formability is reduced, and in the case of Comparative Example 8 in which maleic anhydride-modified polyolefin (D2) is applied instead of the modified polyolefin of the present invention, chemical resistance, thin film formability, and the like are lowered. It can be seen that in Comparative Example 9 in which a small amount of the phosphorus compound of the present invention is applied, thin film formability, etc.
  • Comparative Example 10 in which an excessive amount of the phosphorus compound of the present invention is applied, it can be seen that plating reliability, chemical resistance, etc. are reduced.
  • Comparative Example 11 in which a small amount of the phosphate-based compound (E1) among the phosphorus-based compounds of the present invention (excessive amount of the phosphazene-based compound (E2)) was applied, it can be seen that chemical resistance and the like are lowered, and among the phosphorus-based compounds of the present invention.
  • Comparative Example 12 in which the phosphate-based compound (E1) was applied in an excessive amount (a small amount of the phosphazene-based compound (E2)), it can be seen that the thin film formability and the like deteriorated, and the phosphite-based compound (E3) instead of the phosphorus-based compound of the present invention ), in the case of Comparative Example 13, it can be seen that chemical resistance, thin film formability, etc. are lowered.
  • Comparative Example 13 in which the phosphat

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Abstract

La présente invention concerne une composition de résine thermoplastique comprenant : une résine de polycarbonate ; une résine de polyester modifiée par un glycol ayant une teneur en 1,4-cyclohexanediméthanol d'environ 20 à 100 % en moles dans les constituants diols totaux ; un additif pour structuration directe par laser ; une polyoléfine modifiée comprenant des motifs répétitifs représentés par la formule chimique 1 et des motifs répétitifs représentés par la formule chimique 2 ; un composé phosphoré comprenant un composé phosphate et un composé phosphazène ; et des fibres de verre, le rapport en poids de l'additif pour structuration directe par laser au composé phosphoré étant d'environ 1:0,25 à environ 1:1,20. La composition de résine thermoplastique présente une excellente fiabilité de placage, une excellente résistance au choc, une excellente résistance aux agents chimiques (résistance au choc sur film mince après peinture), une excellente rigidité, une excellente capacité de façonnage d'un film mince, et analogues.
PCT/KR2021/003743 2020-05-27 2021-03-26 Composition de résine thermoplastique pour un procédé de structuration directe par laser et produit moulé la comprenant Ceased WO2021241870A1 (fr)

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